Polycrystalline ZnO:B grown by LPCVD as TCO for thin film silicon solar cells

Conductive zinc oxide (ZnO) grown by low pressure chemical vapor deposition (LPCVD) technique possesses a rough surface that induces an efficient light scattering in thin film silicon (TF Si) solar cells, which makes this TCO an ideal candidate for contacting such devices. IMT-EPFL has developed an in-house LPCVD process for the deposition of nanotextured boron doped ZnO films used as rough TCO for TF Si solar cells. This paper is a general review and synthesis of the study of the electrical, optical and structural properties of the ZnO:B that has been performed at IMT-EPFL. The influence of the free carrier absorption and the grain size on the electrical and optical properties of LPCVD ZnO:B is discussed. Transport mechanisms at grain boundaries are studied. It is seen that high doping of the ZnO grains facilitates the tunnelling of the electrons through potential barriers that are located at the grain boundaries. Therefore, even if these potential barriers increase after an exposition of the film to a humid atmosphere, the heavily doped LPCVD ZnO:B layers show a remarkable stable conductivity. However, the introduction of diborane in the CVD reaction induces also a degradation of the intra-grain mobility and increases over-proportionally the optical absorption of the ZnO:B films. Hence, the necessity to finely tune the doping level of LPCVD ZnO:B films is highlighted. Finally, the next challenges to push further the optimization of LPCVD ZnO:B films for thin film silicon solar cells are discussed, as well as some remarkable record cell results achieved with LPCVD ZnO:B as front electrode.

N/I buffer layer for substrate microcrystalline thin film silicon solar cell

Christophe Ballif, Franz-Josef Haug, Xavier Niquille, Martin Python, Thomas Söderström, Vanessa Terrazzoni-Daudrix

The influence of the substrate surface morphology on the performance of microcrystalline silicon solar cells in the substrate or n-i-p (nip) configuration is studied in this paper. The experiments are carried out on glass substrates coated with naturally textured films of ZnO deposited by low pressure chemical vapor deposition which serves as backcontact and as template for the light trapping texture. The film surface morphology can be modified with a plasma treatment which smoothens the V-shaped valleys to a more U- shaped form. We investigate, first, the influence of different substrates morphologies on the performance of microcrystalline (μc-Si:H) thin film silicon solar cells deposited by very high frequency plasma enhanced chemical vapor deposition. The V-shaped morphologies are found to have strong light trapping capabilities but to be detrimental for the μc-Si:H material growth and lead to degraded open circuit voltage (Voc) and fill factor (FF) of the solar cells. Hence, in Sec., we introduce a buffer layer with a higher amorphous fraction between the n doped and intrinsic layer. Our study reveals that the buffer layer limits the formation of voids and porous areas in the μc- Si:H material on substrates with strong light trapping capabilities. Indeed, this layer mitigates Voc and FF losses which enhances the performance of the μc-Si:H solar cell. Finally, by applying our findings, we report an efficiency of 9% for a nip μc-Si:H thin film silicon cell with a thickness of only 1.2 μm. © 2008 American Institute of Physics.

2008

Optical Layers for Thin-film Silicon Solar Cells

Peter Cuony

In this work we develop and analyze optical layers for use in Micromorph solar cells, a tandem configuration with an amorphous silicon top cell and a microcrystalline silicon bottom cell. The morphology of the front electrode has a decisive role in maximizing the efficiency of a solar cell. To reach a better understanding of the requirements for the front electrode surface, we present a wide range of morphologies that can be obtained with as-grown rough zinc oxide (ZnO) and post-deposition argon plasma surface treatments. We correlate the morphological parameters to light scattering in transmission and reflection, and identify the inclination angles of ZnO pyramids as the most pertinent parameter for thin-film silicon solar cells. We show that there are no reflection losses at the interface between as-grown rough ZnO and silicon, and we quantify the reflection losses for smoother interfaces. With titanium dioxide, produced by reactive magnetron sputtering, we demonstrate that for flat interfaces reflection losses of up to 7.4% can be canceled at 550 nm wavelength. We show that in microcrystalline silicon cells p-type silicon sub-oxide (SiOx) can also be used to reduce reflection losses, and at the same time can act as field-creating window layer. We develop a wide range of mixed-phase SiOx layers and with energy-filtered transmission electron microscopy we reveal the filamentous nanostructure of films produced with high hydrogen dilution of the precursor gas mixture. A partial decoupling of electrical and optical parameters is achieved for such films, where the transparency and the refractive index are determined mostly by the silicon oxide matrix, while sufficient transverse conductivity for the use in solar cells is maintained by few-nanometer-wide silicon filaments. In thin-film silicon solar cells, p-type SiOx~0.5 shows the best results as a window layer with enhanced transparency, while strongly phosphorous-doped n-type SiOx~1 is best suited for use as an intermediate reflecting layer in tandem cells due to a low refractive index of 1.8 with sufficient transverse conductivity. The tunable resistance of doped SiOx layers can be used at various locations in a Micromorph cell to quench shunts or bad diodes in spatially non-uniform devices. Implementation of SiOx with these three functionalities in Micromorph cells has significantly contributed to increasing the best initial efficiency from 11.8% in 2006 to 13.5% in 2010. While rough ZnO front electrodes and SiOx-based intermediate reflecting layers both help to improve Micromorph cell efficiencies, they render the devices more sensitive to water-vapor-induced degradation. With lock-in thermography measurements we demonstrate that water contamination affects mainly the cell borders resulting in non-uniform distribution of the local open circuit voltage. Finally we show how free-carrier absorption and surface plasmon polariton absorption can reduce the reflectivity of the back reflector, and we present preliminary results aimed toward the realization of an absorption-free back reflector making use of polished ZnO and sputtered silver layers.

EPFL2011

Low-Pressure Chemical Vapor Deposited Zinc Oxide Films

Laura Ding

Polycrystalline zinc oxide (ZnO) films, prepared by low-pressure chemical vapor deposition are investigated in this thesis. ZnO belongs to the class of transparent conductive oxide materials, as it is transparent to light from the visible to the near-infrared range and is simultaneously electrically conductive. These two properties allow ZnO films to be integrated in thin-film silicon solar cells, as well as other opto-electronic devices. In particular, thin-film solar cells require a contact layer covering the whole active layer in order to efficiently collect the photogenerated electrical current, and therefore, the film electrode at the front of the cell has to be a window to the sunlight, in addition to being able to transport current. ZnO’s electrical conductivity is usually improved by doping with impurities like boron, but the film transparency is reduced, and consequently, the current that the solar cell can produce decreases. Thus, the first point investigated in this thesis is to find ways to relax the trade-off between transparency and conductivity. Instead of doping, which increases the electron concentration, the electron mobility has to be improved. To do so, the electron transport is first studied and modeled for standard films, in order to better define and understand its limitations. Then, a new way of preparing ZnO bilayer films is shown to lead to enhanced transparency and light scattering, for a maintained conductivity compared to uniformly doped films. Alternatively, various treatments (hydrogen plasma, vacuum annealing and ultraviolet exposure) are tested, all of which reduce the density of defects that cause electron scattering in the ZnO; treated films present an improved conductivity and very high mobilities close to 60 cm2V−1s−1, which corresponds to the mobility value in single crystals of equivalent doping. In addition, these films absorb less than 2% of the visible-to-infrared light, which makes them very promising ultra-transparent electrodes, for solar cells or other applications. For use in thin-film silicon solar cells, two additional criteria have to be met besides trans- parency and conductivity. First, because the front electrode is also the substrate for the deposition of the rest of the cell layers, its surface morphology has to be favorable to the growth of silicon. Moreover, this surface has to present a rough texture capable of diffusing and trapping the light into the cell, and increasing its chance of being absorbed. These charac- teristics can be incompatible, but are nevertheless necessary to reach thin-film solar cells with high efficiencies. So, the second point of interest of this thesis is to adapt the surface of ZnO layers by investigating their preparation method. Combinations of different growth regimes in multilayers are proposed to enable a smoother controllable of the surface without resort to additional etching treatments, leading to improved solar cell electrical performance. Finally, the stability of ZnO films exposed to various conditions that modify their electrical and optical properties is investigated. First, ZnO is exposed to different oxidizing conditions (storage and annealing in air, exposure to moisture, plasma of carbon dioxide). The loss in conductivity from the interaction of the oxygen species with ZnO is characterized by a new infrared spectroscopic method and a hydrogen plasma treatment is investigated as a means to reverse or partially prevent the degradation in conductivity. Then, the effect of simulated sunlight exposure on ZnO film properties in solar cells is investigated. The resistivity of the front ZnO electrode decreases due to ultraviolet light absorption, and the resistivity of the back electrode increases due to the chemisorption of oxygen species, in absence of ultraviolet light. The front electrode transparency is also degraded; this effect is more pronounced for doped ZnO and its impact on the current photogeneration of solar cells is demonstrated. Therefore, a specific optimization of the front and back electrodes appears necessary. This thesis contributes on the one side to an in-depth understanding of the opto-electrical properties of ZnO films prepared by low-pressure chemical vapor deposition. On the other side, the different proposed approaches enable more flexibility in the development of more efficient and stable electrodes, not only for solar cells, but for many other applications such as electroluminescent diodes, flat-panel displays, touch-screens or transparent transistors.